Reversible galvanic battery.



W. MORRISON. REVBRSIBLBGALVANIG BATTERY.

APPLIOATION FILED 00T. 10,1191'0.

' Patented Nov. 15, 1910.

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W. MORRISON. REVERSIBLE GALVANIC BATTERY.

APPLICATION ,FILED 00T- 10, 1910.

Patented Nov. 15, 1910.

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REVERSIBLE GALVAN IG-\BATTEEY. APPLIOATION FILED 00T. 1o, 1910.

976,092.. Patented Nov.15, 1910.

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APPLIOATIGN FILED OQT. 10I 1910.

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APPLICATION FILED 00T- 10, 1910.

Patented Nov. 15, 1910.

6 SHEETS-SHEET 6.

WILLIAM MORRISON, OF DES MOINES, IOWA.

REVERSIBLE GAVLVANIC BATTERY.

aruosa.

Specification of Letters Patent.

Patented Nov. 15, 1910.

Application filed October 10, 1910.. Serial N o. 586,334.

To lall whom fitma/y concern:

Be it knownl that I, WILIAM MORRISON,

a citizen of the United States of America, and resident ot Des Moines, Polk county, Iowa, have invented a certain new and useful Improvement in Reversible Galvanic Batteries, of which the following is a specilication.' v

My invention relates to reversible galvanic batteries,l and more particularl to a `batery in which an alkaline electro yte is use An object of my invention is to construct a reversible battery having a very high elliciency and one which may be charged and discharged a large number of times without any material deterioration of the various elements of my battery.

'A further object is to provide a battery of" very light weight in proportion to the horsepower developed.

`"A further object is to produce an improved battery in'which the positive electrode or negative pole plate is composed of a compound of zinc and chromium such as described in my copending application, Serial-No. 529,187, flied November 22, 1909, and in which the negative electrode or positive pole plate is composed of an oxid of silver and mercury, suchas described in my copending application, Serial No. 531,230, filed Dec. 3, 1909, and in which an electrolyte of potassium hydroxid containing pref erably a small amount of chromium, is used. These and other objects of my invention will be more fully understood by reference to the accompanying drawingsk in which- Figure 1 is a perspective view of a completed battery. Fig. 2 is a plan view of the same. Fig. 3 is a plan view with the cover removed inorder to show the interior construction. Fig. l4 is a longitudinal cross section, with parts broken away in order to more fully show the interior construction. Fig. o5l is a cross sectional view `taken on a plane at ri ht angles to that of Fig. 4. Fig. 6 is a detaied view of one of the grids which make up the negative electrode. Fig. 7 is a detail showing the positive elect-rode. Fig. 8 is a cross` sectionaldetail showing the internal construction or one of the tubes shown in Fig. 7.

Throughout the .drawings likeV reference characters refer to similar parts.

As shown in Fig. l my battery consists 1 of an exterior casing 1, composed of metal or other suitable material. l A suitable cover 2 is employed through which extend the ter minals 3 and upon which is located a suit lable valve 4 and a cover 5 for the tillinoA hole. The interior of this casing is lined with a suitable insulated lining 6 whereby all the parts are completelyA insulated from the metallic casing.

As shown in Figs. 4 and 5, there is located in the bottom of t e casing an improved insulating support. This ysupport comprises a plurality of sections 7 composed of rubber or other suitable material. Each of these sections are of such a length as to fit closely in the casing, as shown 1n Fig. 5, and the various sections are tied together with threaded rods 8 upon which are suitable nuts 9, located on these rods in the manner clearly shown in Fig. 4. Any desired number of these sections may be employed but I have shown seven, which is the same as the number of tubes which compose each positive electrode, as will more fully hereinafter appear. Supported' transversely of these insulating sections are a plurality of. grids in which the active material for the negative Y electrode is held. Thesev grids are constructed in a manner similar to lthat de scribed in my copending application, Serial No. 583,709, tiled Sept. 26, 1910. As fully described in said application, and as shown in Fig. 6, each of the grids consists of two sections 10 and 11. Each of these sections is formed of sheet material, preferably copper,` in which a' plurality stamped out, these openings being formed o openings are' by cutting the material uponthree sides of each opening and then bending back the materialA upon the remaining side so as to form ametallidprojection which extends into the active material of the completed grid. Copper is. especially advantageous for the reasons that it is not rotted by absorbingA mercury, as is nickel; its oXid is electrically conductive; and its oxid is notv soluble in an alkaline solution containing a chromium compound, as is nickel oXid.

In the construction of the completed nega-V tive electrode the active material 'is first placed in the section -10 and then the section 11 pressed down upon the s ame under hlgh pressure. The active material which I prefer to use for my negative electrode which is placed in the Grids just described, is coinposed of an oXid of silver and mercury, which compound is more fully described in my copending application, ff-Serial No. 531,230, referred to above. In the preparation of this active material, I take silver and mercury in the proportion of 1 pound of silver to from 5 to 9 pounds of mercury, and dissolve them in nitric acid. I then add caustic potash in excess of that necessary to precipitate and thus precipitate silver and Y.

I then wash the precipitate mercury oxids. in hot water, preferably containing a little caustic soda or potash, and dry the precipi! tate. This precipitate is then ready to be packed'in the grids as above described.

The positive electrode consists of a suitable active material which is confined in a plurality of tubes 12, such asl shown in Figs. 7 and 8. Each of these tubes is constructed in a manner similarly shown to that in my copending application, Seria-l No. 586,335, filed Oct. 10, 1910. Each tube consists of an interior lining 13 of heavy paper, and

1an exteriorcovering 14y of woven asbestos tubing or other similar material. In order .to strengthen these paper-asbestos tubes,

they may be either Wound with wire or covered with a perforated metal; tube. EX- tending through the center of each tube is a main conductor 15, 'which conductor projects intoA the plug 17 in the bottom of each tube and passes through the plug 16 .which is inserted in the top of each tube.' Care must be taken that the binding Wire is insulated from this internal conductor.

tube is divided into a plurality of sections 'by' means of washers 19 which are placedl Each at suitable distances apart upon the conductors 15. The series of tubes which' go to make 11p/each electrode plate are connected together bya suitable connector 18, as more fu ly described in my copending application. The active'material is placed in these tubes between the washers, and the active ma` terial which I employ is composed of a compound of zinc and chromium mixed with an oXid of mercury, such as is described in my ,copending application Serial .No. 529,187, referred to above. This compound may be obtained by various methods, butby adding an alkaline solution an oXid of mercury is precipitated, which is also thoroughly \vashed, preferably in hot water. The

two precipitates are then thoroughly mixed and the resulting mixture placed in the tubes in the manner described above. Another -method by which I may produce this zinc chromium compound is by taking a suitable quantity of chromium sulfate and thoroughly dissolving this Icompound in hot distilled Water. I` then take a suiiicient quantity ofV Zinc oxid and stir the saine thoroughly in water, preferably by means of an agitator, until the mixture is entirely free from lumps and a thin paste is obtained. Then add to this paste or mixture, while it is in an agitated condition, the chromium sulfate solution mentioned above. The proportions which may be termed a sulfo-chromite.

then pour off the solution from this precipi-I4 tate and add an excess of a strong solution of'hot` caustic potash. This caustic potash acts to form a solution of potassium sulfate' and a precipitate of a zinc-chromium-oxygen compound.- If suitable proportions are used in the first place, this/compound maybe zinc chromite, but when different proporchromium will be obtained. I therefore do not wish to limit myself to zinc ehromite. I then pour off the potassiumy sulfate solution yfrom this zinc-chromium precipitate and wash the precipitatef'several times with hot water in order ,to/remove' all traces of the sulfate. The zinc-chromium compound -which is obtained is then dried in any suit able manner and is then ready to bepacked into the tubes, as above described. y

These positive and negative, electrodes constructed in the manner above described, are placed upon the supports 7 in alternate relation, and are separated by insulating sheets 20, each sheet being constructed in ay manner well known 'i'n the art, and consisting of a sheet of perforated rubber or other similar material, upon which there are a plurality of longitudinal projections 21, whereby the electrodes are thoroughly insulated from each otherand yetthe electrolyte is allowed to pass readily around the same.

All of the negative electrode grids are connected together by a suitable bolt 22, which bolt is connected to one of the terminals 3 by a exible connection 23, as clearly shown `in Fig. 5. Likewise the posiltions are used, other compounds of zinc and .the

v.tiveJ electrodes are connected together by a suitable bolt 24 and a flexible connection 25 extending/t0 the Opposite` terminal 3.

The safety valve t may be of any Well known construction, and I, therefore, do not think it necessary to describe it in detail, as such valves are Well known in the art.

The electrolyte which I prefer to use is composed of otassium hydroxid which con-- tains prefera ly a small amount of chromium. This electrolyte fills the interior ofl the casing to a point just below the topI of the plugs 16 in the tubes 12. These plugs being of insulatin ,materiah prevent the electrolytic actionv rom passing directly to the conductors 15 .and thus in effect prevent a partial short circuit.

In the operation of my battery in the charging anddischarging the same, the following changes take place, as near as I am able to ascertain: The chemical changes, however, are very complicated and accordingly I do not wish to be held -to limit myself to the exact reactions whichr I set forth, but in order to more completely understand the loperation of this battery, I will give the chemical reactions .asv I understand them, after complete and thorough tests and exerimenting with a complete battery. Be-

ore the battery is first charged the positivepole plate consists, as above described, of. oxids of silver and mercury, While the posi-- tive electrode 'or negative pole plate consists of a compound of zinc and chromium mixed with an oxid of mercury. This mercury when reduced by the electrolytic action/ merely acts as an amalgamator ,for the zirr'c/ but is not an active element. On the first charge the silver and mercury in the posi-v tive-pole electrode may take' a higher degree of oxidation. yThe zinc-chromium compound inthe negative-pole electrode is reduced to metallic zinc and potassium chromite, or some other potassium-chromium compound is formed.

Whether or notl all ofthe zinc is reduced to metallic zinc depends upon the-duration of the charge. Thel greater part,Y however, is ordinarily reduced. On the discharge the silver and mercury oxids of the positivepole electrode are again reduced and if thev positive electrode is of suliicient'size and the discharge is carried on for, a` suiicientlength of time, they will be reduced to a mixture .of mercury and silver. Likewise on :the discharge the potassium 4chromite ofv the ,nega- "tive-gple electrode, havlng a `greater aiinity for t e zinc oxid resultin from the, dis. charge .than has Athe -potasslum lhydroxid of ectrolyte,"unites directly-with the zinc okid, to form" the zinc-chromium-oxygen compound and potassium hydroxid in a' concentrated st ate. In this reaction a zincchromium-pot-assium compound may also be formed, 1n which case the potassiumhyv same by any changes which `take place during the charge and discharge. The active material of the' negative-pole electrode, however, during the charge and discharge, undergoes a complete change, and it 1s, therefore, necessary to confine the same in order to prevent it from being forced out into the electrolyte. I have found that if this material is placed in an open grid, during the discharge it will` be forced out through the openings in the grid and be washed away into the electrolyte. i

A very important and essential feature in the construction of the positive electrode is in having the main conductor in the interior ofthe active material, as during the charge Y and discharge of the battery the electrolytic action seeks'vthe best conductor, and, therefore, by my construction this electrolytic action commences on the inside and works out. This methodl of operation is very essential for t-he ro-per operation of this elecc trode, for the o-llowingl-reasons;

The nascent hydrogen combines with the oxygen of the zinc-chromium compound, which forms the active material in thetube and the lpotassium hydroxid combinesfwith the chromium compound of this active ma terial to forma potassium-chromium-oitygen compound. Byy havino' this central conductor, it will be readily seen that theelec'- trolytic action .takes place almostl entirely inside of the tube and works outward, so that lsubstantially all of the active material is acted upon more yquickly and thoroughly. Furthermore, in' the working of this electrode is necessary, during the charge, that there beta concentrated solutionof the otas-.

sium hydroxid inside of the electro e,-in order that this hydroxid may comblne with the chromium of the zinc-chromium compound, under the electrolytic action, in the most effective manner to-form a potassiumchromium compound, sothat the zinc may be reduced to the metallicstate. `If an external `conductorwere used, the hydrogen would be liberated on the exterior of the tube to a great ez'rtent, would escape through the solution into the air, and would notacteffectively u on the zinc-chromium compound to re uce the same. Likewise the ypotassium oxid would unite with the water in the electrolyte to form otassium hydroxid, which would be in t emain body of electrolyte instead of being conned as a .concentrated solution with the active material. It will accordingly be seen that with this arrangement a' roper operation of my electrode would not be attained.

It is further noted that it is necessary that there be a concentrated solution of otassium hydroxid inside of the tube. T is concentrated ,solution is necessary to obtain a powerful discharge of the battery`,.in addition to the reasons above noted. This solution y.in the t-ube is more concentrated than that of the main electrolyte, and it is for that reason that it is very important that I the active material be confined Within the orous tubes described, so that there Will very little free circulationLof the potassiumi hydroxid from the inside-to the'outside of the tube, as underrthese conditions it would be impossible to maintain the strong solution necessary u on the inside of the tube. Furthermore,` find itbest to form the tubes cylindrical, as in this shape they are better able to resist the pressurel from the inside, which is caused by the changein the condition of the material during the under consi erable high current -tia ly charged, but for thebest operation the rate of charging should be malntained slightly higher than thel rate at which it is desired to discharge the battery.

A further important feature of the construction of my lmproved electrode is in the provision of the plugs 4 and 5 through which the conductor 6 passes. Thesey plugs protect the ends of the rod so that the tubes may be surrounded with the electrolyte up to a point above the top ci the tube, and yet a very small amount of the currentwill pass directly to the upper endof this conductor on account of the same being protected by the insulating plug. The lowers end of the rod is protected in the same manner by the plug 4.

I claim:

1. A reversible galvanic battery compris-l mg anegative-pole electrode containing an oxidizable metal and a chromium compound,

a mpositive-pole electrode.V containing silver a .mercury, and an alkaline electrolyte.

I 2. Areversible galvanicnbatutery ing a negative-pole electrode containing an oxidizable metal and a chromium-oxygen compound, a pos1t1Ve-pole electrode con- .tainlng silver and mercury, and an alkaline mercury, a positive-pole electrode containling silver and mercury, and an alkaline electrolyte. l

4. A reversible galvanic battery compris-v ing a negative-pole electrode containing an oxidizable. metal, a chromium-oxygen compound and mecury, a positive-pole electrode containing silver andmercury, and an alkalineelectrolyte. y

A reversible galvanic battery comprising a negative-pole electrode containing zinc and a chromium-oxygen compound, a positive-pole electrode vcontaining silver and mercury, and an alkaline electrolyte.

6. A reversible galvanic battery comprising a negative-pole electrode containing zinc, a chromium-oxygen compound and mercury, a ositive-pole electrode containing silver and) mercury, and an alkaline electrolyte.

7. A reversible galvanic battery comprisin a ne ative- )ole electrode containing an oxidizab e metai and a chromium compound, a positive-pole electrode containing mercury, and an alkaline electrolyte.

8. A reversible galvanic battery comprising a 11e ative-pole electrode containing an oxidizab e metal and a chromium-oxygen compouncha positive-pole electrode containing mercury, and an alkaline electrolyte.

9. A reversible galvanic battery comprising a negative-pole electrode containing an oxidizable metal, a chromium compound and mercury, a positive-pole electrode containing mercury, and an alkaline electrolyte.

10. A reversible galvanic battery comprising a negative-pole electrode containing an oxidizable metal, a chromium-oxygen compound and mercury, a positive-pole electrode containing mercury, and an alkaline electrolyte. n

11. A reversible galvanic battery comprising a negative-poleelectrode containing zinc and a chromium-.oxygen compound, a positive-pole electrode containmg mercury, and

an alkaline electrolyte.

12. A reversible galvanic battery comprising a negative-pole electrode containing zinc, a chromium-oxygen compound and mercury, a. positive-pole electrode containing mercury, and an alkaline electrolyte. f

13. In a reversible galvanic battery, an alkaline electrolyte, and a positive-pole elec'- trode comprising a copper conductor or support and active material containing oxids of mercury and silver.

14. In a reversible (galvanic battery, an alkaline electrolyte, an av pos'tive-pole electrode comprising a conductor or support of l hydrate electrolyte,

copper and an active material containing oxid of mercury.

15. In a reversible galvanic battery, an alkaline electrolyte containing chromium, and a positive-pole electrode having a conductor or support of copper.

16. In a' reversible galvanic battery, an alkaline electrolyte, a ositive-pole electrode having active material containing mercury and another metal, anda negative trode insoluble in the electrolyte.

17. In 'a reversible galvanic battery, an alkaline electrolyte, a ositive-pole electrode -having active material containing mercury pole-elecand silver, and a` negative-pole electrode insoluble in the electrolyte. 18. In a reversible battery, an alkalinea negative-pole electrode containing zinc, apositive-pole electrode, and means for preventing solution of the zinc in the electrolytef 19. In a reversible battery, an alkalinehydrateelectrolyte, a negative-pole electrode containing zinc and a compound capable of renderingzinc o'xiol or liydroxid substantially insoluble in the electrolyte, a positivepole electrode, and a porous separator impermeable to zinc oXid or liydroxid between said electrodes.

Signed by Ine at Washington, District of Columbia this 8th day of October 19,10.

IVILLIAM MORRISON. Witnesses:

Jos. H. BLAoKWooD, H. A. SWENARTON. 

